JPH03204876A - Pyrazole derivative, production thereof and herbicide comprising same derivative as active ingredient - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (R is lower alkyl, lower alkenyl, lower alkynyl or lower alkoxy lower alkyl). USE:A herbicide showing selectivity between crops and weeds and excellent herbicidal effects. PREPARATION:A compound shown by formula II is reacted with a compound shown by the formula R-X (X is Cl, Br, I, p-toluenesulfonyloxy or methanesulfonyloxy) to give a compound shown by formula I. The reaction is carried out at 0-100 deg.C for 0.5-10 hours. The amounts of the compound shown by formula III and the base are 1-2 equivalents and 1-2 equivalents based on 1 equivalent compound shown by formula II. The solvents to be used are hexane, butane, benzene, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel pyrazole derivative, a method for producing the same, and a herbicide containing the same as an active ingredient.

<Prior art> Until now, Japanese Patent Publication No. 19958-1995, Japanese Patent Publication No. 42-1997
Certain pyrazole derivatives are described in Publication No. 14833 and the like. Furthermore, European Publication No. 334055 describes that some pyrazole derivatives have herbicidal activity.

<Problem that the invention seeks to solve> However, these compounds have insufficient herbicidal efficacy,
It is difficult to say that this is necessarily satisfactory because selectivity between crops and weeds is poor.

In view of this situation, the present inventors have conducted various studies and found that the pyrazole derivative represented by the following general formula (I) has excellent herbicidal efficacy with few drawbacks as described above. The present invention was based on the discovery that the compound has the following properties and exhibits excellent selectivity between crops and weeds.

That is, the present invention is directed to the general formula [wherein R represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, or a lower alkoxy lower alkyl group]. The present invention provides a pyrazole derivative represented by (hereinafter referred to as the compound of the present invention), a method for producing the same, and a herbicide containing the same as an active ingredient.

The compound of the present invention, which has a methyl group at the 3-position of the pyrazole ring, a difluoromethyl group at the 4-position, and a chlorine atom at the 5-position, exhibits excellent herbicidal efficacy and selectivity between crops and weeds.

The compound of the present invention is a compound represented by the formula and the general formula R-X (III) [wherein, X is a chlorine atom, a bromine atom, an iodine atom, or p-]
It represents a luenesulfonyloxy group or a methanesulfonyloxy group, and R has the same meaning as above. ] It can be produced by reacting with the compound shown below.

The above reaction is usually carried out in a solvent in the presence of a base, with a reaction temperature ranging from 0 to 100°C and a reaction time ranging from 0 to 100°C.
The reaction time is 5 to 10 hours, and the amount of reagent used in the reaction is determined by the formula (
If), the general formula [I[r
] The amount of the compound shown is 1 to 2 equivalents, and the amount of the base is 1 to 2 equivalents.

The solvents used include aliphatic hydrocarbons such as hexane, heptane ligroin, petroleum ether, benzene,
Aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene, and dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, and diethylene glycol dimethyl ether, acetone, Ketones such as methyl ethyl ketone, methyl isobutyl ketone, isophorone, and cyclohexanone; fatty acids such as formic acid, acetic acid, and oleic acid; esters such as ethyl formate, ethyl acetate, butyl acetate, and diethyl carbonate; nitrides such as nitroethane and nitrobenzene; acetonitrile; Nitriles such as isobutyronitrile, tertiary amines such as pyridine, triethylamine, N,N-diethylaniline, tributylamine, N-methylmorpholine, acid amides such as formamide, N,N-dimethylformamide, acetamide, dimethyl Examples include sulfur compounds such as sulfoxide and sulfolane, liquid ammonia, water, and mixtures thereof. Examples of bases include organic bases such as pyridine, triethylamine, and N,N-diethylaniline, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and sodium hydride, and sodium methoxide and sodium ethoxide. Examples include alkali metal alkoxides.

After the reaction is complete, the reaction solution is poured into water and the resulting crystals are collected by filtration, or conventional post-treatments such as organic solvent extraction and concentration are carried out.
If necessary, the desired compound of the present invention can be obtained by purification by operations such as chromatography, distillation, and recrystallization.

Note that some of the compounds of the present invention have optical isomers derived from asymmetric carbon atoms, and it goes without saying that all of these optical isomers are also included in the present invention.

Next, a method for producing a compound represented by the formula CM, which is a raw material compound for the compound of the present invention, will be explained.

The compound represented by formula (If) can be produced according to the following route.

The compound represented by formula [IV] can be produced by reacting 2,4-difluorophenylhydrazine and ethyl acetoacetate in acetic acid at 50 to 100'C.

The compounds of the present invention have excellent herbicidal efficacy and exhibit excellent selectivity between grass crops and weeds. That is, the compound of the present invention is
Various weeds that are problematic in the treatment of foliage and soil in upland fields, such as buckwheat weeds, Japanese knotweed, purslane, chickweed, white radish, blue radish, Japanese radish, Japanese radish, shepherd's shepherd's shepherd's shepherd's shepherd's nape,
Broad-leafed weeds such as Japanese commonweed, American golden deer, field pansies, Japanese violet, American morning glory, Malva morning glory, Convolvulus, Japanese staghorn, Japanese staghorn, Japanese Physalis, Japanese staghorn, Japanese fir, sunflower, dog mottle, corn marigold, etc., barnyard grass, Japanese commonweed, Green foxtail,
The compound of the present invention has a herbicidal effect on grass weeds such as Japanese grasshopper, sycamore, sycamore, oat, oat, seiban sorghum, grasshopper, and sorghum, as well as weeds of the family Cyperaceae such as dayflower, and weeds of the cyperaceae family such as japonica japonica. Some of them do not cause harmful effects on major crops such as corn, wheat, barley, rice, soybean, cotton, and sugar beet, especially on corn and soybean.

In addition, the compound of the present invention can be applied to various weeds that are problematic in the flooding treatment of rice fields, such as grass weeds such as Japanese grasshopper, broad-leaved weeds such as acetifolia, kiwi, cypressweed, and chickweed, and cyperaceae weeds such as bulrush and cyperus. It has a herbicidal effect on grasses such as P. elegans, P. elegans, and P. elegans, and does not cause any harmful effects on rice.

When using the compound of the present invention as an active ingredient of a herbicide,
It is usually mixed with solid carriers, liquid carriers, surfactants, and other formulation auxiliaries to formulate emulsions, wettable powders, suspensions, granules, etc.

These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.02 to 80%, preferably 0.05 to 70%.

Examples of solid carriers include fine powders or granules such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, walnut shell powder, urea, ammonium sulfate, and synthetic hydrous silicon oxide. Examples of liquid carriers include aromatic hydrocarbons such as xylene and methylnaphthalene, alcohols such as Impropatol, ethylene glycol, and cellosolve, ketones such as acetone, cyclohexanone, and isohorn, vegetable oils such as soybean oil and cottonseed oil, and dimethyl sulfoxide, N,
Examples include N-dimethylformamide, acetonitrile, water and the like.

Surfactants used for emulsification, dispersion, wetting layers, etc. include alkyl sulfate salts, alkyl sulfonate salts, alkylaryl sulfonate salts, dialkyl sulfosuccinate salts, polyoxyethylene alkylaryl ether phosphate salts, etc. Anionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbicun fatty acid ester, etc. etc.

As formulation adjuvants, lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC
(carboxymethylcellulose), PAP (isopropyl acid phosphate), and the like.

The compound of the present invention is usually formulated and treated with soil, foliage, or flooding before or after the emergence of weeds. In particular, soil treatment is preferred. Soil treatment includes soil surface treatment, soil mixing treatment, etc., and foliage treatment includes treatment from above the plant body, as well as local treatment that treats only weeds so that they do not attach to crops.

Further, by mixing it with other herbicides, it can be expected to increase the herbicidal efficacy. Furthermore, it can be used in combination with insecticides, acaricides, nematicides, fungicides, plant growth regulators, fertilizers, soil conditioners, and the like.

The compound of the present invention can be used in rice fields, fields, orchards, pastures,
It can be used as an active ingredient in lawns, forests or non-agricultural lands.

When the compound of the present invention is used as an active ingredient of a herbicide, the amount to be treated will vary depending on weather conditions, formulation form, treatment time, method, location, target weeds, target crops, etc., but usually 1.
0.01 g - 100 g per are, preferably
0.05g to 50g, and emulsions, wetting agents, suspending agents, etc. are usually used in a prescribed amount of 1 liter to 10 liters per are (if necessary, auxiliary agents such as spreading agents are added).
It is treated by diluting it with water, and granules and the like are usually treated as they are without any dilution.

In addition to the above-mentioned surfactants, the spreading agents include polyoxyethylene resin acid (ester), lignin sulfonate,
Examples include abietate, dinaphthylmethane disulfonate, and paraffin.

<Effects of the Invention> The compound of the present invention has excellent herbicidal efficacy against various weeds that are problematic in soil treatment and foliage treatment of upland fields, as well as in flooding treatment of paddy fields, and has excellent weed control properties between major crops and weeds. Since it exhibits selectivity, it can be used for various purposes as an active ingredient in herbicides.

<Example> Next, the present invention will be explained in more detail by giving production examples, reference examples, formulation examples, and test examples.

First, a manufacturing example will be shown.

Production Example Synthesis of Compound (3) 5-chloro-4-difluoromethyl-1-[7-fluoro-2H-1,4-benzoxazin-3(4H)-one-6-yl]-3-methyl-pyrazole 2.0g was dissolved in 10g of dimethylformamide, and 0.8g of propargyl bromide and 1.6g of potassium carbonate were added thereto.
Heated at 0-80°C for 3 hours. The reaction solution was poured into water, and the resulting crystals were collected by filtration, washed with water, dried, and purified by column chromatography to obtain 1.0 g of the desired compound as white crystals.

Melting point 181-183°C 'H-N) JRδ (ppm) (CDCf,, 6
0MHz)2,05(t, J=2Hz, LH),
2.20 (s, 3H), 4.50 (d, J=2
Hz, 2H), 4.51(s, 3)1), 6
．． 40 (t, J=54Hz, IH), 6.78 (
d, J=11Hz, IH), 6.98(d, J
=7Hz, LH) Table 1 shows the compounds of the present invention produced according to the above production example.

Table 1 Next, production examples of production intermediates of the compounds of the present invention are shown as reference examples.

Reference Example 1 Production method of compound [■] Compound [IV] 2. 10g of methylformamide
and add 3.5 g of phosphorus chloride to it to make 80
Heated at ~100°C for 3 hours. After the reaction was completed, the reaction solution was poured into water, and the crystals formed were collected by filtration, washed with water, dried, and purified by column chromatography to obtain 1.0 g of the desired compound as white crystals.

Melting point 121-122°C Reference example 2 Manufacturing method of compound [■] Compound (V) 1. og was dissolved in 10 g of dichloromethane, 3.8 g of N,N-diethylaminosulfur trifluoride was added thereto, and the mixture was stirred overnight at room temperature. After the reaction was completed, the reaction solution was poured into water, branched, washed with water, dried, concentrated, and purified by column chromatography to obtain 0.7 g of the desired compound as white crystals.

Melting point 89-91°C Reference example 3 Process for producing compound [■] 0.7g of compound [VI] was dissolved in 10g of concentrated sulfuric acid, 0.4g of concentrated nitric acid was added to this after cooling with water, and the mixture was heated at 10°C or less.
Stir for hours. After the reaction was completed, the reaction solution was poured into water, and the resulting crystals were collected by filtration, washed with water, dried, and purified by column chromatography to obtain 0.7 g of the desired compound as white crystals.

Melting point 81-83°C Reference example 4 Process for producing compound [■] 0.5 g of compound [■] was dissolved in 10 g of dioxane, and 1.5 g of potassium fluoride and 0.0 g of butyl glycolate were added to the solution.
．． 5 g was added and refluxed for 3 hours. After the reaction was completed, the reaction solution was poured into water, subjected to solvent extraction with ether, washed with water, dried, concentrated, and purified by column chromatography to obtain 0.6 g of the desired compound as white crystals.

Melting point 142-144°C Reference example 5 Process for producing compound (I heated for an hour. After the reaction was completed, 10 g of ethyl acetate was added to the reaction solution, insoluble materials were removed by filtration, washed with water, dried, and concentrated.
Purification was performed by column chromatography to obtain 0.2 g of the desired compound as white crystals.

Melting point: 270-274°C Next, formulation examples will be shown. The compounds of the present invention are indicated by compound numbers in Table 1. Parts are parts by weight.

Formulation Example 1 50 parts each of the compounds (1) to (4) of the present invention, 3 parts of calcium lignosulfonate, 2 parts of sodium lauryl sulfate, and 45 parts of synthetic hydrous silicon oxide are thoroughly ground and mixed to obtain a wettable powder.

Formulation Example 2 Compounds of the present invention (1) to (4), 5 parts each, 14 parts of polyoxyethylene styrylphenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 25 parts of xylene, and 50 parts of cyclohexanone are thoroughly mixed to form an emulsion. get.

Formulation Example 3 2 parts each of the compounds (3) and (4) of the present invention, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay were thoroughly ground and mixed, and water was added. After thoroughly kneading, the mixture is granulated and dried to obtain granules.

Formulation Example 4 Compounds of the present invention (3) and (4), 25 parts each, 3 parts polyoxyethylene sorbitan monooleate, 3 parts CMC,
A suspension is obtained by mixing 69 parts of water and wet milling until the particle size is 5 microns or less.

Next, a test example will be shown. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used for comparison are indicated by the compound symbols in Table 2.

Table 2 In addition, the evaluation of herbicidal efficacy and phytotoxicity is based on whether the germination and growth conditions of the test plants (weeds and crops) at the time of the survey have no or almost no difference compared to untreated plants.
The test plants are classified into 6 stages from 0 to 5, and are shown as Oll, 2.3.4.5.

Test Example 1 A circular plastic pot with a diameter of 10 an and a depth of 10 nm was filled with field soil, and barnyard grass, oats, morning glory, and Japanese crocodile were sown and covered with soil. The test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the emulsion was applied to the soil surface using a small sprayer. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 3.

Table 1 Test Example 2 A circular plastic pot with a diameter of 10 cm and a depth of 10 AO was filled with field soil, and barnyard grass, oats, radish, and Japanese radish were sown and grown in a greenhouse for 10 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water containing a spreading agent equivalent to 10 liters per are, and the foliage was treated from above the plant using a small sprayer. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 4.

Table 4 Table 4 Test Example 3 A cylindrical plastic pot with a diameter of 8 ann and a depth of 12 countries was filled with rice paddy soil, and seeds of Japanese millet and broad-leaved weeds (Azaena, Azalea, Chickweed) were mixed in at a depth of 1 to 2 cm. . After being flooded into paddy fields, they were grown in a greenhouse. Six days later (at the beginning of each weed's emergence), the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with 5 milliliters of water, and the emulsion was applied to the water surface. After treatment, the plants were grown in a greenhouse for 20 days and their herbicidal efficacy was investigated. The results are shown in Table 5.

Test Example 4 Upland soil was filled in a vat with an area of 33 x 23 a 11 and a depth of 1 lan, and soybeans, corn, rice, Japanese morning glory, Japanese radish, Japanese Physalis, Japanese Physalis, and Japanese foxtail were sown, and the soil was covered with soil to a thickness of 1 to 2 ao. The test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the emulsion was applied to the soil surface using a small sprayer. After treatment, the plants were grown in a greenhouse for 20 days, and their herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 6.

Table 6. After treatment, the plants were grown in a greenhouse for 27 days, and their herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 7.

Table 7 Test Example 5 A vat with an area of 33 x 23 Ci and a depth of 11 cm was filled with field soil, and wheat, barley, sugar beet, Japanese knotweed, chickweed, giant dogfish, white locust, and field pansy were sown and covered with soil to a thickness of 1 to 2 cm. The test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the soil surface was treated with a small sprayer. Pack the soil, sow soybeans, corn, morning glory, Japanese radish, Japanese phyllocarp, and golden deer.1
It was grown for 8 days. Thereafter, the test compound was made into an emulsion according to Formulation Example 2, a predetermined amount of the emulsion was diluted with water equivalent to 10 liters per are, and the emulsion was uniformly applied from above the plant to the surface of the leaves using a small sprayer. At this time, the growth conditions of weeds and crops vary depending on the grass species, but the growth status of weeds and crops is 1 to 4 leaves, and the height of the plant is 2.
It was ~12an. Herbicidal efficacy and phytotoxicity were investigated 20 days after treatment. The results are shown in Table 8. This test was conducted in a greenhouse throughout the entire period.

Table 8 Test Example 7 A 115,000a Wagner pot was filled with paddy soil and planted with Japanese millet and broad-leaved weeds (Azaena, Kikashigusa, Chickweed)
seeds were mixed in at a depth of 1 to 2 AO. After flooding to create a paddy field, three-leaf stage rice was further transplanted and grown in a greenhouse. After 11 days (second vegetable stage of Japanese millet), Formulation Example 2
Make an emulsion of the test compound according to
And so.

After treatment, the plants were grown in a greenhouse for 20 days, and their herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 9. Note that for two days from the day after the treatment, water leaked in an amount equivalent to a water depth of 3 cm per day.

Table 9 Test Example 8 A vat with an area of 11 x 15 al and a depth of 7 ann was filled with field soil, and soybeans, red radish, Japanese cabbage, and physalis were sown, and the soil was covered with soil to a thickness of 1 to 2 ao. Formulation example 2
The test compound was made into an emulsion according to the method described above, a predetermined amount of the emulsion was diluted with water equivalent to lθ liters per are, and the mixture was applied to the soil surface using a small sprayer.

After treatment, the plants were grown in a greenhouse for 20 days, and their herbicidal efficacy and phytotoxicity were investigated. The results are shown in Table 10.

No. 0 table

Claims (3)

[Claims] (1) General formula▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R represents a lower alkyl group, a lower alkenyl group, a lower alkynyl group, or a lower alkoxy lower alkyl group. ] A pyrazole derivative represented by (2) A compound represented by the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. , X represents a base atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group or a methanesulfonyloxy group. ] The method for producing a pyrazole derivative according to claim 1, characterized by reacting the pyrazole derivative with a compound represented by the following. (3) A herbicide containing the pyrazole derivative according to claim 1 as an active ingredient.